CN105264619A - Metal nitride material for thermistor, manufacturing method for same, and film-type thermistor sensor - Google Patents

Metal nitride material for thermistor, manufacturing method for same, and film-type thermistor sensor Download PDF

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CN105264619A
CN105264619A CN201480031428.0A CN201480031428A CN105264619A CN 105264619 A CN105264619 A CN 105264619A CN 201480031428 A CN201480031428 A CN 201480031428A CN 105264619 A CN105264619 A CN 105264619A
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film
thermistor
metal nitride
nitride materials
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CN105264619B (en
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藤田利晃
田中宽
长友宪昭
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Mitsubishi Materials Corp
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    • H01C7/04—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient
    • H01C7/042—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient mainly consisting of inorganic non-metallic substances
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    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0005—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with at least one oxide and at least one of carbides, nitrides, borides or silicides as the main non-metallic constituents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
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    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
    • G01K7/16—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using resistive elements
    • G01K7/22—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using resistive elements the element being a non-linear resistance, e.g. thermistor
    • G01K7/223—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using resistive elements the element being a non-linear resistance, e.g. thermistor characterised by the shape of the resistive element
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
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    • H01C1/14—Terminals or tapping points or electrodes specially adapted for resistors; Arrangements of terminals or tapping points or electrodes on resistors
    • H01C1/142—Terminals or tapping points or electrodes specially adapted for resistors; Arrangements of terminals or tapping points or electrodes on resistors the terminals or tapping points being coated on the resistive element
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/075—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thin film techniques
    • H01C17/12—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thin film techniques by sputtering
    • H—ELECTRICITY
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    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/006—Thin film resistors
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    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/008—Thermistors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/04—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient
    • H01C7/041—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient formed as one or more layers or coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/04—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient
    • H01C7/042—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient mainly consisting of inorganic non-metallic substances

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Abstract

The present invention is a metal nitride material used for a thermistor, comprising a metal nitride represented by the general formula: Mx(Al1-vSiv)y(N1-wOw)z (wherein M represents at least one of Ti, V, Cr, Mn, Fe, and Co; 0.0 < v < 0.3; 0.70 <= y/(x+y) <= 0.98; 0.45 <= z <= 0.55; 0 < w <= 0.35; and x + y + z = 1), such that the crystal structure of the same is a single phase of hexagonal wurtzite-type. A manufacturing method for this metal nitride material for a thermistor comprises a deposition step which forms a film by performing reactive sputtering within a nitrogen- and oxygen-containing atmosphere using a M-Al-Si alloy sputtering target (wherein M represents at least one of Ti, V, Cr, Mn, Fe, and Co).

Description

Thermistor metal nitride materials and manufacture method thereof and film-type thermistor (temperature) sensor
Technical field
The present invention relates to a kind of can under non-firing condition the thermistor metal nitride materials of direct formation of film at surface on film etc. and manufacture method thereof and film-type thermistor (temperature) sensor.
Background technology
The thermistor material being used in temperature sensor etc. is in order to high accuracy, high sensitivity and require higher B constant.In the past, this thermistor material was generally the transition metal oxide (referenced patent document 1 ~ 3) of Mn, Co, Fe etc.Further, in these thermistor materials, in order to obtain stable thermistor characteristic, the heat treatment such as to burn till of more than 550 DEG C is needed.
Further, except the thermistor material be made up of metal oxide described above, such as, in patent documentation 4, propose by with general formula: M xa yn z(wherein, M represents at least one in Ta, Nb, Cr, Ti and Zr, and A represents at least one in Al, Si and B.0.1≤x≤0.8,0 < y≤0.6,0.1≤z≤0.8, x+y+z=1) the thermistor material that forms of the nitride that represents.And, in this patent documentation 4, only record following material as embodiment, be Ta-Al-N based material, and be set as 0.5≤x≤0.8,0.1≤y≤0.5,0.2≤z≤0.7, x+y+z=1.This Ta-Al-N based material by the material containing above-mentioned element is used as target, and is making containing carrying out sputtering in nitrogen atmosphere.Further, as required, the film of gained is heat-treated with 350 ~ 600 DEG C.
Further, as different from thermistor material one example, such as, in patent documentation 5, propose by with general formula: Cr 100-x-yn xm y(wherein, M is one or more the element being selected from Ti, V, Nb, Ta, Ni, Zr, Hf, Si, Ge, C, O, P, Se, Te, Zn, Cu, Bi, Fe, Mo, W, As, Sn, Sb, Pb, B, Ga, In, Tl, Ru, Rh, Re, Os, Ir, Pt, Pd, Ag, Au, Co, Be, Mg, Ca, Sr, Ba, Mn, Al and rare earth element, and crystalline texture is mainly bcc structure or is mainly the line and staff control of bcc structure and A15 type structure.0.0001≤x≤30,0≤y≤30,0.0001≤x+y≤50) the strain transducer resistive film material that forms of the nitride that represents.This strain transducer resistive film material, being all set in the composition of 30 below atom % by nitrogen quantity x, accessory ingredient element M amount y, according to the resistance variations of Cr-N base strain resistor film sensors, for measurement and the conversion of strain and stress.Further, this Cr-N-M based material as the target of the material containing above-mentioned element etc., and carries out reactive sputtering and is produced in the film forming atmosphere containing above-mentioned accessory ingredient gas.Further, as required, the film of gained is heat-treated with 200 ~ 1000 DEG C.
Patent documentation 1: Japanese Patent Publication 2000-068110 publication
Patent documentation 2: Japanese Patent Publication 2000-348903 publication
Patent documentation 3: Japanese Patent Publication 2006-324520 publication
Patent documentation 4: Japanese Patent Publication 2004-319737 publication
Patent documentation 5: Japanese Patent Publication 10-270201 publication
In above-mentioned technology in the past, leave following problem.
In recent years, study the exploitation of the film-type thermistor (temperature) sensor forming thermistor material on resin film, expecting to develop can the thermistor material of direct formation of film at surface on film.That is, expect by using film and obtain pliability thermistor (temperature) sensor.And then, expect to develop the very thin thermistor (temperature) sensor with 0.1mm left and right thickness, but usually use the baseplate material that have employed the potteries such as aluminium oxide in the past, if thickness is such as thinned to 0.1mm, then there is the very fragile and easy problem such as broken, but expect by using film and obtain very thin thermistor (temperature) sensor.
But, the usual heat resisting temperature of the film be made up of resin material is lower is less than 150 DEG C, even be known as the polyimides of the higher material of heat resisting temperature, owing to also only having the thermal endurance of about 200 DEG C, be difficult to be suitable for when therefore applying heat treatment in the formation process of thermistor material.Above-mentioned oxide thermosensitive resistor material in the past, in order to realize desired thermistor characteristic, needing more than 550 DEG C burn till, there is the problem that cannot realize the film-type thermistor (temperature) sensor of direct formation of film at surface on film.Therefore, expect to develop can under non-firing condition the thermistor material of direct formation of film at surface, even but the thermistor material recorded in above-mentioned patent documentation 4, in order to obtain desired thermistor characteristic, be necessary the film of gained to heat-treat with 350 ~ 600 DEG C as required.Further, this thermistor material, in the embodiment of Ta-Al-N based material, although obtain B constant: the material of about 500 ~ 3000K, do not have the description about thermal endurance, and the thermal reliability of nitride material system is indefinite.
And, the Cr-N-M based material of patent documentation 5 be B constant less be less than 500 material, and, if do not implement the heat treatment of more than 200 DEG C less than 1000 DEG C, then cannot guarantee the thermal endurance within 200 DEG C, therefore there is the problem that cannot realize the film-type thermistor (temperature) sensor of direct formation of film at surface on film.Therefore, expect to develop can under non-firing condition the thermistor material of direct formation of film at surface.
Summary of the invention
The present invention completes in view of described problem, its object is to provide one under non-firing condition, on film etc., and high-fire resistance can be had and the higher thermistor metal nitride materials of reliability and manufacture method and film-type thermistor (temperature) sensor by direct formation of film at surface.
Inventor is conceived to comprise the nitride based of Al and conducts in-depth research in nitride material.Find that AlN or the Si part as insulator replaces the (Al of Al position, Si) N is difficult to obtain best thermistor characteristic (B constant: about 1000 ~ 6000K), but by replacing Al position or (Al with the specific metallic element improving conduction, Si) position, and be set to specific crystalline texture, thus under non-firing condition, obtain good B constant and thermal endurance.
Therefore, the present invention obtains according to above-mentioned result of study, adopts following structure to solve described problem.
That is, the thermistor metal nitride materials involved by the 1st invention is the metal nitride materials for thermistor, it is characterized in that, by with general formula: M x(Al 1-vsi v) y(N 1-wo w) z(wherein, M represents at least one in Ti, V, Cr, Mn, Fe and Co.0.0 < v < 0.3,0.70≤y/ (x+y)≤0.98,0.45≤z≤0.55,0 < w≤0.35, x+y+z=1) metal nitride that represents forms, and its crystalline texture is the single-phase of the wurtzite-type of hexagonal crystal system.
This thermistor metal nitride materials is by with general formula: M x(Al 1-vsi v) y(N 1-wo w) z(wherein, M represents at least one in Ti, V, Cr, Mn, Fe and Co.0.0 < v < 0.3,0.70≤y/ (x+y)≤0.98,0.45≤z≤0.55,0 < w≤0.35, x+y+z=1) metal nitride that represents forms, and its crystalline texture is the single-phase of the wurtzite-type of hexagonal crystal system, therefore under non-firing condition, obtain good B constant, and there is high-fire resistance.Especially containing aerobic (O), thermal endurance is improved further by being filled up the effects such as oxygen is imported between nitrogen defect in crystallization or lattice by oxygen thus.
In addition, if above-mentioned " y/ (x+y) " (namely, (Al+Si)/(M+Al+Si)) be less than 0.70, then can not get the single-phase of wurtzite-type, the crystalline phase with the coexisting phase of NaCl type phase or only NaCl type can be become, sufficient high resistance and high B constant cannot be obtained.
Further, if above-mentioned " y/ (x+y) " (that is, (Al+Si)/(M+Al+Si)) is greater than 0.98, then resistivity is very high, shows high insulating properties, therefore cannot be suitable for as thermistor material.
Further, if above-mentioned " z " (that is, (N+O)/(M+Al+Si+N+O)) is less than 0.45, then nitrogenize amount is less, therefore can not get the single-phase of wurtzite-type, can not get sufficient high resistance and high B constant.
And, if above-mentioned " z " (that is, (N+O)/(M+Al+Si+N+O)) is greater than 0.55, then cannot obtain the single-phase of wurtzite-type.This situation result from wurtzite-type single-phase in, do not have the stoichiometric proportion during defect on nitrogen position to be 0.5 (, N/ (M+Al+Si+N)=0.5) situation and the stoichiometric proportion of oxygen when filling up on nitrogen position defect be completely the situation of 0.5 (that is, (N+O)/(M+Al+Si+N+O)=0.5).With regard to the z amount being greater than 0.5, the quantitative accuracy of the light element (nitrogen, oxygen) in the situation that the oxygen between lattice that results from is imported into and XPS analysis.
Further, in this research, above-mentioned " w " (that is, O/ (N+O)) cannot be obtained and be greater than the single-phase of the wurtzite-type of 0.35.If this situation considers following situation, be then appreciated that namely at w=1 and y/ (x+y)=0 time, rutile-type (M1) O 2phase, corundum type (M2) 2o 3phase, spinel-type (M3) 3o 4phase (wherein, represent M1=Ti, M2=V, Cr, Fe, M3=Mn, Co), at w=1 and y/ (x+y)=1 and V=0 time, be corundum type Al 2o 3phase, at w=1 and y/ (x+y)=1 and V=1 time, be rutile-type SiO 2phase.If known w value increases, oxygen amount increases relative to nitrogen quantity, be then difficult to obtain wurtzite-type single-phase, in this research, finds, to O/ (N+O)=0.35, to obtain wurtzite-type single-phase.
And, if above-mentioned " v " (that is, Si/ (Al+Si)) is more than 0.3, then cannot obtain the film of the single-phase crystallinity excellence of wurtzite-type.If this situation considers following situation, be then appreciated that namely at v=1 and y/ (x+y)=1 and w=1 time, for having phenacite (Be 2siO 4) Si of type structure 3n 4phase, at v=1 and y/ (x+y)=1 and w=0 time, be the SiO of christobalite type, tridymite type, quartz type 2phase.
The feature of the thermistor metal nitride materials involved by the 2nd invention is, in the 1st invention, is formed as membranaceous, and is the column crystallization extended along the direction perpendicular to the surface of described film.
That is, this thermistor metal nitride materials, due to the column crystallization for extending along the direction perpendicular to the surface of film, therefore the crystallinity of film is higher, obtains high-fire resistance.
The feature of the thermistor metal nitride materials involved by the 3rd invention is, in the 1st or the 2nd invention, is formed as membranaceous, and on the direction on the surface perpendicular to described film, the orientation of c-axis is better than the orientation of a axle.
That is, this thermistor metal nitride materials, because the orientation of c-axis is better than the orientation of a axle on the direction on the surface perpendicular to film, obtains higher B constant compared with therefore stronger with a axle orientation situation, and also excellent to the reliability of thermal endurance.
The feature of the film-type thermistor (temperature) sensor involved by the 4th invention is to possess: insulating properties film; Thin-film thermistor portion, this insulating properties film is formed by the thermistor metal nitride materials of arbitrary invention in the 1st to the 3rd; And a pair pattern electrode, be at least formed in upside or the downside in described thin-film thermistor portion.
Namely, in this film-type thermistor (temperature) sensor, owing to being formed with thin-film thermistor portion by the thermistor metal nitride materials of arbitrary invention in the 1st to the 3rd on insulating properties film, therefore by the high B constant that formed under non-firing condition and the higher thin-film thermistor portion of thermal endurance, the insulating properties film that the thermal endurances such as resin film are lower can be used, and obtain there is the slim of good thermistor characteristic and pliability thermistor (temperature) sensor.
And, usually use the baseplate material that have employed the potteries such as aluminium oxide in the past, if thickness is such as thinned to 0.1mm, then there is the very fragile and easy problem such as broken, but in the present invention owing to using film, therefore, it is possible to obtaining thickness is such as the very thin film-type thermistor (temperature) sensor of 0.1mm.
The manufacture method of the thermistor metal nitride materials involved by the 5th invention is the method for the thermistor metal nitride materials of arbitrary invention in manufacture the 1st to the 3rd, it is characterized in that, have and use M-Al-Si alloy sputtering targets (wherein, M represents at least one in Ti, V, Cr, Mn, Fe and Co) in the atmosphere of nitrogenous and oxygen, carry out sputtering (reactive sputtering) and the film formation process of film forming.
That is, in the manufacture method of this thermistor metal nitride materials, in the atmosphere of nitrogenous and oxygen, reactive sputtering and film forming is carried out, therefore, it is possible to will by above-mentioned M owing to using M-Al-Si alloy sputtering targets x(Al 1-vsi v) y(N 1-wo w) zthe thermistor metal nitride materials of the present invention formed carries out film forming under non-firing condition.
The feature of the manufacture method of the thermistor metal nitride materials involved by the 6th invention is, in the 5th invention, the sputtering pressure in described reactive sputtering is set smaller than 0.67Pa.
Namely, in the manufacture method of this thermistor metal nitride materials, due to the sputtering pressure in reactive sputtering is set smaller than 0.67Pa, therefore, it is possible to the orientation being formed in c-axis on the direction perpendicular to the surface of film is better than the film of the thermistor metal nitride materials involved by the 3rd invention of the orientation of a axle.
According to the present invention, reach following effect.
That is, according to thermistor metal nitride materials involved in the present invention, by with general formula: M x(Al 1-vsi v) y(N 1-wo w) z(wherein, M represents at least one in Ti, V, Cr, Mn, Fe and Co.0.0 < v < 0.3,0.70≤y/ (x+y)≤0.98,0.45≤z≤0.55,0 < w≤0.35, x+y+z=1) metal nitride that represents forms, its crystalline texture is the single-phase of the wurtzite-type of hexagonal crystal system, therefore under non-firing condition, obtain good B constant, and there is high-fire resistance.And, according to the manufacture method of thermistor metal nitride materials involved in the present invention, owing to using M-Al-Si alloy sputtering targets (wherein, M represents at least one in Ti, V, Cr, Mn, Fe and Co) in the atmosphere of nitrogenous and oxygen, carry out reactive sputtering and film forming, therefore, it is possible to will by above-mentioned M x(Al, Si) y(N, O) zthe thermistor metal nitride materials of the present invention formed carries out film forming under non-firing condition.And, according to film-type thermistor (temperature) sensor involved in the present invention, owing to being formed with thin-film thermistor portion by thermistor metal nitride materials of the present invention on insulating properties film, therefore using the lower insulating properties film of the thermal endurances such as resin film and obtain there is the slim of good thermistor characteristic and pliability thermistor (temperature) sensor.And baseplate material is not if thinning just very fragile and hold breakable pottery, but resin film, therefore obtain the very thin film-type thermistor (temperature) sensor of thickness 0.1mm.
Accompanying drawing explanation
Fig. 1 is in an execution mode of thermistor metal nitride materials involved in the present invention and manufacture method and film-type thermistor (temperature) sensor, represents that Ti-(Al+Si)-(N+O) of the compositing range of thermistor metal nitride materials is ternary inorganic solution.
Fig. 2 is in the present embodiment, represents the stereogram of film-type thermistor (temperature) sensor.
Fig. 3 is in the present embodiment, represents the stereogram of the manufacture method of film-type thermistor (temperature) sensor with process sequence.
Fig. 4 is in the embodiment of thermistor metal nitride materials involved in the present invention and manufacture method and film-type thermistor (temperature) sensor, represents front view and the vertical view of the film evaluation element of thermistor metal nitride materials.
Fig. 5 is in embodiment involved in the present invention and comparative example, represents the chart of the relation between 25 DEG C of resistivity and B constant.
Fig. 6 is in embodiment involved in the present invention and comparative example, represents the chart of the relation between (Al+Si)/(Ti+Al+Si) ratio and B constant.
Fig. 7 is in embodiment involved in the present invention, represents the chart of the relation between O/ (O+N) ratio and N/ (Ti+Al+Si+N) ratio.
Fig. 8 is in embodiment involved in the present invention, represents the chart of X-ray diffraction (XRD) result when c-axis orientation being set to (Al+Si)/(Ti+Al+Si)=0.88 is stronger.
Fig. 9 is in embodiment involved in the present invention, represents the chart of X-ray diffraction (XRD) result when a axle orientation being set to (Al+Si)/(Ti+Al+Si)=0.87 is stronger.
Figure 10 is in embodiment involved in the present invention, represents the section S EM photo of the embodiment that c-axis orientation is stronger.
Figure 11 is in embodiment involved in the present invention, represents the section S EM photo of the embodiment that a axle orientation is stronger.
Embodiment
Below, referring to figs. 1 to Fig. 3, an execution mode of thermistor metal nitride materials involved in the present invention and manufacture method and film-type thermistor (temperature) sensor is described.In addition, in the accompanying drawing used in the following description, be set to the size that can identify or easily identify in order to Jiang Gebu and suitably change engineer's scale as required.
The thermistor metal nitride materials of present embodiment is the metal nitride materials for thermistor, by with general formula: M x(Al 1-vsi v) y(N 1-wo w) z(wherein, M represents at least one in Ti, V, Cr, Mn, Fe and Co.0.0 < v < 0.3,0.70≤y/ (x+y)≤0.98,0.45≤z≤0.55,0 < w≤0.35, x+y+z=1) metal nitride that represents forms, and its crystalline texture is wurtzite-type (the space group P6 of hexagonal crystal system 3mc (No.186)) single-phase.
Such as, during M=Ti, the thermistor metal nitride materials of present embodiment is by with general formula: Ti x(Al 1-vsi v) y(N 1-wo w) zthe metal nitride that (0.0 < v < 0.3,0.70≤y/ (x+y)≤0.98,0.45≤z≤0.55,0 < w≤0.35, x+y+z=1) represents is formed, and its crystalline texture is the single-phase of the wurtzite-type of hexagonal crystal system.Namely, as shown in Figure 1, this thermistor metal nitride materials is forming in the region that surrounds of some A, B, C, D in ternary inorganic solution for having by Ti-(Al+Si)-(N+O), and crystalline phase is the metal nitride of wurtzite-type.
In addition, each ratio of components (x, y, z) (atm%) of above-mentioned some A, B, C, D is A (x, y, z=13.5,31.5,55.0), B (x, y, z=0.9,44.1,55.0), C (x, y, z=1.1,53.9,45.0), D (x, y, z=16.5,38.5,45.0).
As mentioned above, the crystalline texture of wurtzite-type is the space group P6 of hexagonal crystal system 3mc (No.186), Ti, Al, Si belong to same atoms position, are in so-called admittedly molten state (such as, Ti 0.1al 0.88si 0.02during N, Ti, Al, Si are present in same atoms position with the probability of 10%, 88%, 2%).Wurtzite-type is got (Ti, Al, Si) N 4tessarace connecting structure, the position closest to (Ti, Al, Si) position is N (nitrogen), and (Ti, Al, Si) gets nitrogen four-coordination.
In addition, except Ti, V (vanadium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt) can be present in the atom site identical with Ti equally in above-mentioned crystalline texture, can become the element of M.Effective ionic radius is the physics value being usually used in grasping interatomic distance, if use the literature value of the ionic radius of the Shannon particularly known, then can infer the V (Al that also can obtain wurtzite-type in theory, Si) N, Cr (Al, Si) N, Mn (Al, Si) N, Fe (Al, Si) N, Co (Al, Si) N.
The effective ionic radius (reference papers R.D.Shannon, ActaCrystallogr., Sect.A, 32,751 (1976)) of each ionic species of Si, Al, Ti, V, Cr, Mn, Fe, Co is shown in the following table 1.
[table 1]
Wurtzite-type is four-coordination, if observe the effective ionic radius of four-coordination about M, be then Co < Fe < Mn during divalent, be Al < Fe during 3 valency, be Si < Co, Mn < Cr < Ti during 4 valency, during 5 valency, become Cr < V.According to these results, think (Al, Si, Co) < Fe < Mn < Cr < (V, Ti) and Si < Co (magnitude relationship of the ionic radius of Ti and V or Co and Al or Si and Al cannot be differentiated).Wherein, the data of four-coordination are different respectively due to valence mumber, therefore cannot carry out strict comparison, so, if observe hexa-coordinate (MN when being fixed on 3 valency ion as a reference 6octahedra) data, then known ionic radius becomes Al < Co < Fe < Mn < Cr < V < Ti (in table 1, HS represents high spin state, and LS represents low spin state).According to above result, known ionic radius becomes (Al, Si) < Co < Fe < Mn < Cr < V < Ti.
The present invention passes through the wurtzite-type (Al of insulator, Si) (the Al of N, Si) position is substituted by Ti etc. and carries out charge-carrier dopant, and conduction increases, and obtains thermistor characteristic thus, but such as by (Al, Si) when position is substituted by Ti, because the effective ionic radius of this side of Ti is greater than (Al, Si), result (Al, Si) increases with the average ionic radius of Ti.As a result, can infer that interatomic distance increases, and lattice constant increases.
By X ray data validation to by the increase Al position of (Al, Si) N being substituted by the lattice constant that Ti etc. causes.Such as, in the X ray diffracting data described later (Fig. 7) when being set to M=Ti, compared with the peak value of AlN, the peak value of (Ti, Al, Si) N is more displaced to side, low angle, and according to its result, known lattice constant is greater than AlN.Further, when being set to M=Cr, also by X ray diffracting data, compared with the peak value of AlN, the peak value of (Cr, Al, Si) N is more displaced to side, low angle, according to its result, confirms lattice constant and is greater than AlN.Further, owing to being equivalent to the X-ray diffraction peak value not division of AlN, therefore in conjunction with its result, known have Ti and Si in the solid solution of Al position, or have Cr and Si in the solid solution of Al position.In this test, think that main reason that lattice constant increases is because the ionic radius of the M such as Ti is greater than the ionic radius of Al, therefore average ionic radius increases (although valence mumber is different along with the increase of (M+A)/(M+A+Al) ratio, but be difficult to think that the ionic radius of Al is greater than the ionic radius of Si according to table 1, in this experiment, think that the main cause that lattice constant increases measures by M such as Ti the effect increasing and cause).
In addition, in order to maintain wurtzite-type, the M such as Ti are to (Al, solid solution boundary is had in the substitution amount of Si) position, if (namely Ti/ (Ti+Al+Si) is greater than about 0.3, if (Al+Si)/(Ti+Al+Si) is less than 0.7), then more easily generate NaCl type compared with wurtzite-type.
And, because the ionic radius of V, Cr, Mn, Fe, Co gets (Al, Si) value and between Ti, therefore from the view point of the lattice constant of wurtzite-type, think compared with Ti replace (Al, Si) position, (Al is replaced with V, Cr, Mn, Fe, Co, Si) during position, due to less relative to the increase of identical substitution amount lattice constant, therefore more easily wurtzite-type crystalline texture is maintained.V, Cr, Mn, Fe, Co also have 3d electronics, 4s electronics in the same manner as Ti, can carry out charge-carrier dopant in (Al, Si) position.In addition, in an embodiment, during M=Cr, confirm and generate wurtzite-type crystalline texture.
The thermistor metal nitride materials of present embodiment is formed as membranaceous, and is the column crystallization extended along the direction perpendicular to the surface of described film.And preferably on the direction on the surface perpendicular to film, the orientation of c-axis is better than the orientation of a axle.
In addition, on the direction (film thickness direction) on the surface perpendicular to film, judge that a axle orientation (100) is comparatively strong or c-axis orientation (002) is stronger, it is the orientation utilizing X-ray diffraction (XRD) to investigate crystal axis, according to the peak intensity ratio of (100) (representing the hkl index of a axle orientation) with (002) (representing the hkl index of c-axis orientation), when " peak intensities of (100) "/" peak intensity of (002) " is less than 1, be set to c-axis orientation stronger.
Then, the film-type thermistor (temperature) sensor of the thermistor metal nitride materials employing present embodiment is described.As shown in Figure 2, this film-type thermistor (temperature) sensor 1 possesses: insulating properties film 2; Thin-film thermistor portion 3, this insulating properties film 2 is formed by above-mentioned thermistor metal nitride materials; And a pair pattern electrode 4, be at least formed in thin-film thermistor portion 3.
Above-mentioned insulating properties film 2 is such as formed as banded by polyimide resin sheet.In addition, as insulating properties film 2, can also be PET: polyethylene terephthalate, PEN: Polyethylene Naphthalate etc.
Above-mentioned a pair pattern electrode 4 such as forms pattern by the laminated metal membrane of Cr film and Au film, and has a pair comb electrode portion 4a of the comb-like pattern configured with mutually opposing state in thin-film thermistor portion 3 and leading section and be connected to these comb electrode portion 4a and base end part is configured at the end of insulating properties film 2 and a pair rectilinear extension 4b extended.
Further, on the base end part of a pair rectilinear extension 4b, the lead division as lead-in wire is formed with the plated portions 4c such as plating Au.One end that material etc. is bonded to lead-in wire is welded at this plated portions 4c.And except the end of insulating properties film 2 comprising plated portions 4c, on this insulating properties film 2, pressurizing binding has polyimide cover layer film 5.In addition, by printing, the resin material layer of polyimides or epoxy is formed on insulating properties film 2, to replace polyimide cover layer film 5.
With reference to figure 3, below the manufacture method of the manufacture method of this thermistor metal nitride materials and the film-type thermistor (temperature) sensor 1 of use the method is described.
First, the manufacture method of the thermistor metal nitride materials of present embodiment has film formation process, described film formation process uses M-Al-Si alloy sputtering targets (wherein, M represents at least one in Ti, V, Cr, Mn, Fe and Co) in the atmosphere of nitrogenous and oxygen, carry out reactive sputtering and film forming.
Further, preferably the sputtering pressure in above-mentioned reactive sputtering is set smaller than 0.67Pa.
And, preferably after above-mentioned film formation process, irradiate nitrogen plasma to formed film.
More specifically, as shown in (b) of Fig. 3, on the insulating properties film 2 of the polyimide film of the thickness shown in (a) of such as Fig. 3 50 μm, by the thin-film thermistor portion 3 formed by the thermistor metal nitride materials of above-mentioned present embodiment of reactive sputtering method film forming 200nm.
During M=Ti, sputtering condition is now such as final vacuum: 5 × 10 -6pa, sputtering pressure: 0.4Pa, target drop into power (power output): 300W, and under the mixed-gas atmosphere of Ar gas+nitrogen+oxygen, are set to nitrogen partial pressure: 19.8%, oxygen partial pressure: 0.2%.Further, metal mask is used to be that desired size forms thin-film thermistor portion 3 by thermistor metal nitride materials film forming.In addition, preferably nitrogen plasma is irradiated to formed thin-film thermistor portion 3.Such as, in vacuum degree: 6.7Pa, power output: 200W and N 2under gas atmosphere, nitrogen plasma is made to be irradiated to thin-film thermistor portion 3.
Then, by sputtering method, such as, form the Cr film of 20nm, form the Au film of 200nm further.And, thereon with after excellent coating machine coating anti-corrosion liquid, at 110 DEG C, carrying out preliminary drying 1 point 30 seconds, after utilizing exposure device photosensitive, remove unwanted part with developer solution, within 5 minutes, carrying out pattern formation by drying after at 150 DEG C.Then, by commercially available Au etchant and Cr etchant, wet etching is carried out to unwanted electrode part, as shown in (c) of Fig. 3, peeled off by resist and form the pattern electrode 4 with desired comb electrode portion 4a.In addition, pattern electrode 4 can be pre-formed on insulating properties film 2, and on its comb electrode portion 4a film forming thin-film thermistor portion 3.Now, the comb electrode portion 4a of pattern electrode 4 is formed in the downside in thin-film thermistor portion 3.
Then, as shown in (d) of Fig. 3, such as, the polyimide cover layer film 5 with binding agent of thickness 50 μm is positioned on insulating properties film 2, and utilizes pressuring machine pressurize 10 minutes with 2MPa at 150 DEG C and make it bond.And, as shown in (e) of Fig. 3, in the end of rectilinear extension 4b, such as, form the Au film of 2 μm by Au electroplate liquid and form plated portions 4c.
In addition, when making multiple film-type thermistor (temperature) sensor 1, on the large-scale thin slice of insulating properties film 2, after thin-film thermistor portion 3 as multiple in above-mentioned formation and pattern electrode 4, cut into each film-type thermistor (temperature) sensor 1 from a large thin slice simultaneously.
So, the thinner film-type thermistor (temperature) sensor 1 such as size being set to 25 × 3.6mm, thickness is set to 0.1mm is obtained.
The thermistor metal nitride materials of present embodiment like this is by with general formula: M x(Al 1-vsi v) y(N 1-wo w) z(wherein, M represents at least one in Ti, V, Cr, Mn, Fe and Co.0.0 < v < 0.3,0.70≤y/ (x+y)≤0.98,0.45≤z≤0.55,0 < w≤0.35, x+y+z=1) metal nitride that represents forms, and its crystalline texture is wurtzite-type (the space group P6 of hexagonal crystal system 3mc (No.186)) single-phase, therefore under non-firing condition, obtain good B constant, and there is high-fire resistance.Especially containing aerobic (O), thermal endurance is improved further by being filled up the effects such as nitrogen defect in crystallization by oxygen thus.
Further, this thermistor metal nitride materials is owing to being the column crystallization extended along the direction perpendicular to the surface of film, and therefore the crystallinity of film is higher, and obtains high-fire resistance.
And this thermistor metal nitride materials is on the direction on the surface perpendicular to film, and the orientation of c-axis is better than the orientation of a axle, compared with situation stronger with a axle orientation thus, obtain higher B constant.
In the manufacture method of the thermistor metal nitride materials of present embodiment, owing to using M-Al-Si alloy sputtering targets (wherein, M represents at least one in Ti, V, Cr, Mn, Fe and Co) in the atmosphere of nitrogenous and oxygen, carry out reactive sputtering and film forming, therefore, it is possible to will by above-mentioned M x(Al, Si) y(N, O) zthe above-mentioned thermistor metal nitride materials formed carries out film forming under non-firing condition.
Therefore, in the film-type thermistor (temperature) sensor 1 of thermistor metal nitride materials employing present embodiment, owing to being formed with thin-film thermistor portion 3 by above-mentioned thermistor metal nitride materials on insulating properties film 2, therefore by the high B constant that formed under non-firing condition and the higher thin-film thermistor portion 3 of thermal endurance, the insulating properties film 2 that the thermal endurances such as resin film are lower can be used, and obtain there is the slim of good thermistor characteristic and pliability thermistor (temperature) sensor.
And, usually use the baseplate material that have employed the potteries such as aluminium oxide in the past, if thickness is such as thinned to 0.1mm, then there is the very fragile and easy problem such as broken, but owing to can use film in the present embodiment, therefore, it is possible to obtaining thickness is such as the very thin film-type thermistor (temperature) sensor of 0.1mm.
Embodiment
Then, about thermistor metal nitride materials involved in the present invention and manufacture method thereof and film-type thermistor (temperature) sensor, with reference to figure 4 to Figure 11, the embodiment specifically described by making according to above-mentioned execution mode carries out the result evaluated.
The making > of < film evaluation element
As embodiments of the invention and comparative example, the film evaluation element 121 shown in following construction drawing 4.In addition, in following various embodiments of the present invention, following element is produced.That is, when being set to M=Ti, Ti is employed x(Al, Si) y(N, O) zthe element of thermistor metal nitride, when being set to M=Cr, employ Cr x(Al, Si) y(N, O) zthe element of thermistor metal nitride.
First, utilize reactive sputtering method, use the Ti-Al-Si alloys target of various ratio of components, Cr-Al-Si alloys target, on the Si wafer of band heat oxide film becoming Si substrate S, form the thin-film thermistor portion 3 of the thermistor metal nitride materials formed with the various ratio of componentss shown in table 2 of thickness 500nm.Sputtering condition is now final vacuum: 5 × 10 -6pa, sputtering pressure: 0.1 ~ 1Pa, target drop into power (power output): 100 ~ 500W, and under the mixed-gas atmosphere of Ar gas+nitrogen+oxygen, change nitrogen partial pressure into 10 ~ 100%, oxygen partial pressure are changed into 0 ~ 3% and make.
Then, in above-mentioned thin-film thermistor portion 3, formed the Cr film of 20nm by sputtering method, form the Au film of 200nm further.And, with after spin coater coating anti-corrosion liquid on it, at 110 DEG C, carrying out preliminary drying 1 point 30 seconds, after utilizing exposure device photosensitive, remove unwanted part with developer solution, within 5 minutes, carrying out pattern formation by drying after at 150 DEG C.Then, by commercially available Au etchant and Cr etchant, wet etching is carried out to unwanted electrode part, peeled off by resist and form the pattern electrode 124 with desired comb electrode portion 124a.Further, sheet is cut to and as the film evaluation element 121 of the evaluation of B constant and heat-resistance test.
In addition, as a comparison, for Ti x(Al, Si) y(N, O) zratio of components in scope of the present invention, the outer and comparative example that crystallographic system is different makes similarly and evaluates.
The evaluation > of < film
(1) composition analysis
For the thin-film thermistor portion 3 obtained by reactive sputtering method, carry out elementary analysis with x-ray photoelectron spectroscopy (XPS).In this XPS, sputtered by Ar, in the sputter face of degree of depth 20nm from most surface, implement quantitative analysis.Its result is shown in table 2.In addition, represent with " atom % " with the ratio of components in following table.For a part of sample, implement the quantitative analysis in the sputter face of degree of depth 100nm from most surface, confirm in the scope of quantitative accuracy with the composition that the sputter face of degree of depth 20nm is identical.
In addition, above-mentioned x-ray photoelectron spectroscopy (XPS) using x-ray source as MgK α (350W), logical can: 58.5eV, measuring interval: 0.125eV, angle: 45deg is taken out to the photoelectron in test portion face, analyzed area is about condition under implement quantitative analysis.In addition, about quantitative accuracy, the quantitative accuracy of N/ (M+Al+Si+N+O), O/ (M+Al+Si+N+O) is ± 2%, (Al+Si) quantitative accuracy of/(M+Al+Si) was ± 1% (wherein, M represents at least one in Ti, V, Cr, Mn, Fe and Co).
(2) ratio resistance measures
For the thin-film thermistor portion 3 obtained by reactive sputtering method, be determined at the ratio resistance at 25 DEG C by four-terminal method.Its result shown in table 2 and table 3.
(3) B constant measuring
In thermostat, measure 25 DEG C of film evaluation element 121 and the resistance value of 50 DEG C, calculate B constant by the resistance value of 25 DEG C and 50 DEG C.Its result shown in table 2 and table 3.Further, thermistor into being with negative temperature characteristic is confirmed from 25 DEG C and the resistance value of 50 DEG C.
In addition, the B constant calculating method in the present invention is tried to achieve by following formula by 25 DEG C and 50 DEG C of respective resistance values as above-mentioned.
B constant (K)=ln (R25/R50)/(1/T25-1/T50)
R25 (Ω): the resistance value at 25 DEG C
R50 (Ω): the resistance value at 50 DEG C
T25 (K): 298.15K represents 25 DEG C with absolute temperature
T50 (K): 323.15K represents 50 DEG C with absolute temperature
As can be known from these results, such as, during M=Ti, Ti x(Al, Si) y(N, O) zratio of components in the axonometric projection of the ternary system shown in Fig. 1, in the region surrounded by some A, B, C, D, namely, in whole embodiments in the region becoming " 0.0 < v < 1.0,0.70≤y/ (x+y)≤0.98,0.45≤z≤0.55,0 < w≤0.35, x+y+z=1 ", reach resistivity: the thermistor characteristic of 100 more than Ω cm, B constant: more than 1500K.
According to the above results, the chart of the resistivity at expression shown in Figure 5 25 DEG C and the relation between B constant.Further, the chart of the relation between expression shown in Figure 6 (Al+Si)/(Ti+Al+Si) ratio and B constant.According to these charts, in (Al+Si)/(Ti+Al+Si)=0.7 ~ 0.98 and the region of (N+O)/(Ti+Al+Si+N+O)=0.45 ~ 0.55, crystallographic system is the high resistance and the region of high B constant that the single-phase material of the wurtzite-type of the hexagonal crystal ratio resistance value that can realize at 25 DEG C is 100 more than Ω cm, B constant is more than 1500K.In addition, in the data of Fig. 6, relative to identical (Al+Si)/(Ti+Al+Si) ratio, it is because the nitrogen quantity in crystallization is different with oxygen amount that B constant produces deviation, or because the lattice defect amounts such as nitrogen defect, oxygen defect are different.
Comparative example 2 shown in table 2 is the region of (Al+Si)/(Ti+Al+Si) < 0.7, and crystallographic system becomes the NaCl type of cubic crystal.So, in the region of (Al+Si)/(Ti+Al+Si) < 0.7, the ratio resistance value at 25 DEG C is less than 100 Ω cm, and B constant is less than 1500K, for low resistance and the region of low B constant.
Comparative example 1 shown in table 2 is the region that (N+O)/(Ti+Al+Si+N+O) is less than 40%, and metal becomes the crystalline state of nitrogenize deficiency.This comparative example 1, neither wurtzite-type neither NaCl type, but the state of the non-constant of crystallinity.Further, known in these comparative examples, B constant and resistance value are all very little, close to metal behavior.
In addition, in embodiment shown in table 3 during M=Cr, by being set to Al/ (Cr+Al+Si)=0.7 ~ 0.98, and (N+O)/(Cr+Al+Si+N+O)=0.45 ~ 0.55, also obtain wurtzite-type hexagonal crystal, and obtain high resistance and the thermistor characteristic of high B constant.
(4) film X-ray diffraction (qualification of crystalline phase)
By grazing incidence X-ray diffraction (GrazingIncidenceX-rayDiffraction), the thin-film thermistor portion 3 utilizing reactive sputtering method to obtain is carried out to the qualification of crystalline phase.This film X-ray diffraction is small angle x-ray diffraction (SAXD) experiment, pipe ball is set to Cu, incidence angle is set to 1 degree, and the scope in 2 θ=20 ~ 130 degree measures.For a part of sample, incidence angle is set to 0 degree, and the scope in 2 θ=20 ~ 100 degree measures.
Its result, in the region of (Al+Si)/(Ti+Al+Si) >=0.7, for wurtzite-type phase (hexagonal crystal, the phase identical with AlN), in the region of (Al+Si)/(Ti+Al+Si)≤0.66, for NaCl type phase (cubic crystal, the phase identical with TiN).Further, thinking in 0.66 < (Al+Si)/(Ti+Al+Si) < 0.7, is the crystalline phase that wurtzite-type phase coexists mutually with NaCl type.
In addition, during M=Cr, also confirming in the region of (Al+Si)/(Cr+Al+Si) >=0.7, is wurtzite-type phase.
So at Ti x(Al, Si) y(N, O) zin system, high resistance and the region of high B constant are present in the wurtzite-type phase of (Al+Si)/(Ti+Al+Si)>=0.7.In addition, in an embodiment of the present invention, impurity phase is not confirmed, single-phase for wurtzite-type.
In addition, comparative example shown in table 21 is as above-mentioned, and crystalline phase, neither NaCl type phase neither wurtzite-type phase, fubaritic in this test.Further, these comparative examples, due to the non-constant width of peak width of XRD, are therefore the material of the non-constant of crystallinity.This is presumably because because of electrical characteristics close to metal behavior, therefore become nitrogenize deficiency and dysoxidative Metal Phase.
[table 2]
[table 3]
Then, embodiments of the invention are all the film of wurtzite-type phase, and orientation is comparatively strong, therefore use XRD investigation in the crystal axis in the direction (film thickness direction) perpendicular to Si substrate S in a axle orientation and c-axis orientation which axle orientation stronger.Now, in order to investigate the orientation of crystal axis, measure the peak intensity ratio of (100) (representing the hkl index of a axle orientation) and (002) (representing the hkl index of c-axis orientation).
In addition, even if confirm film forming under identical membrance casting condition, on polyimide film, to be formed with the single-phase of wurtzite-type similarly.Further, even if confirm under identical membrance casting condition, film forming is on polyimide film, and orientation is also constant.
One example of the XRD distribution of the embodiment that c-axis orientation shown in Figure 8 is stronger.This embodiment is (Al+Si)/(Ti+Al+Si)=0.88 (wurtzite-type, hexagonal crystal), incidence angle is set to 1 degree to measure.As seen from these results, in this embodiment, the intensity of (002) becomes very strong compared with (100).
One example of the XRD distribution of the embodiment that a axle orientation shown in Figure 9 is stronger.This embodiment is (Al+Si)/(Ti+Al+Si)=0.87 (wurtzite-type, hexagonal crystal), incidence angle is set to 1 degree to measure.As seen from these results, in this embodiment, the intensity of (100) becomes very strong compared with (002).
In addition, confirm (*) in chart be from device peak value and carry the peak value of Si substrate of heat oxide film, be not the peak value of sample main body or the peak value of impurity phase.Further, incidence angle is set to 0 degree and implements symmetrical mensuration, confirming its peak value can disappear, confirm its for from device peak value and carry the peak value of Si substrate of heat oxide film.
Then, about the embodiments of the invention as wurtzite-type material, associating between crystalline texture with electrical characteristics is compared in more detail.
As shown in table 2, relative to the material of (Al+Si)/(Ti+Al+Si) than approximate ratio, there is the material perpendicular to the crystal axis that the degree of orientation in the direction of real estate is stronger to be the material of the embodiment of c-axis and described crystal axis the be embodiment of a axle.
Relatively, if known (Al+Si)/(Ti+Al+Si) is than roughly the same, then compared with stronger with a axle orientation material, the B constant of this side of material that c-axis orientation is stronger is larger.
And, relative to (Al+Si)/(Ti+Al+Si) than and the material of Si/ (Al+Si) ratio more approximate than both, have the material perpendicular to the crystal axis that the degree of orientation in the direction of real estate is stronger to be the material of the embodiment of c-axis and described crystal axis the be embodiment of a axle.Time relatively, if also known Si/ (Al+Si) is than identical, then compared with stronger with a axle orientation material, the B constant of this side of material that c-axis orientation is stronger is larger.
Further, if be conceived to N amount (N/ (Ti+Al+Si+N+O)), then, compared with the known material stronger with a axle orientation, the nitrogen quantity of this side of material that c-axis orientation is stronger is bigger.And if be conceived to O amount (O/ (N+O)), then, compared with the known material stronger with c-axis orientation, the oxygen amount of this side of material that a axle orientation is stronger is bigger.From this result, the sample that N/ (Ti+Al+Si+N+O) is fewer, O/ (N+O) amount is more.Further, the oxygen amount showing c-axis oriented material is less.
The evaluation > of < crystal habit
Then, as an example of the crystal habit represented in the cross section in thin-film thermistor portion 3, shown in Figure 10, embodiment ((Al+Si)/(Ti+Al+Si)=0.88 of about film forming 520nm on the Si substrate S of band heat oxide film, wurtzite-type, hexagonal crystal, c-axis orientation is stronger) the section S EM photo in thin-film thermistor portion 3.Further, the section S EM photo in the thin-film thermistor portion 3 of another embodiment shown in Figure 11 (hexagonal crystal, a axle orientation is stronger for (Al+Si)/(Ti+Al+Si)=0.87, wurtzite-type).
The sample of these embodiments uses the sample of Si substrate S cleavage fracture.Further, for the photo of 45° angle degree oblique view.
As from this photo, embodiments of the invention are formed by the column crystallization of densification.That is, the appearance that the crystallization of column grows along the direction perpendicular to real estate is observed.In addition, confirm be with heat oxide film Si substrate S on carry out film forming with the thickness of 200nm, 500nm, 1000nm respectively time, also formed by the column crystallization of densification as described above.
In addition, about the size of the column crystallization in figure, in the embodiment that the c-axis orientation of Figure 10 is stronger, particle diameter is length is about 520nm.Further, in the embodiment that a axle orientation of Figure 11 is stronger, particle diameter is length is about 510nm.In addition, particle diameter is now the diameter of the column crystallization in real estate, and length is the length (thickness) of the column crystallization in direction perpendicular to real estate.
If the length-width ratio of column crystallization to be defined as (length) ÷ (particle diameter), then the present embodiment has the larger length-width ratio of more than 10.Think that the particle diameter of column crystallization is less, film becomes fine and close thus.In addition, confirm be with heat oxide film Si substrate S on carry out film forming with the thickness of 200nm, 500nm, 1000nm respectively time, also formed by the column crystallization of densification as described above.
< heat resistant test evaluates >
In embodiment shown in table 2 and a part for comparative example, in air 125 DEG C, resistance value before and after the heat resistant test of 1000h and B constant evaluate.Its result is shown in table 4.In addition, as more also evaluating the comparative example based on Ta-Al-N based material in the past.And, as a reference, illustrate for not carrying out reactive sputtering containing in the nitrogen of oxygen and the mixed-gas atmosphere of Ar gas in table 4 in the lump, and formation carry out the result of heat resistant test similarly based on the reference example 1 (wurtzite-type, hexagonal crystal, c-axis orientation are stronger) in the thin-film thermistor portion 3 of Ti-(Al+Si)-N based material.
As can be known from these results, although Al concentration and nitrogen concentration different, when the comparative example of Ta-Al-N system is compared with the embodiment of the B constant with same degree amount, Ti x(Al, Si) y(N, O) zbe that the resistance value climbing of this side, B constant climbing are all less, thermal endurance when observing with the electrical property change before and after heat resistant test is for Ti x(Al, Si) y(N, O) zbe that this side is more excellent.In addition, embodiment 3,4 is the material that c-axis orientation is stronger, and embodiment 8 is the material that a axle orientation is stronger.If compare both, then, compared with stronger with a axle orientation embodiment, the resistance value climbing of the embodiment that c-axis orientation is stronger is less, and thermal endurance slightly improves.
And, known based on not being better than comparative example containing the thermal endurance of the reference example 1 of Ti-(the Al+Si)-N based material of aerobic energetically, but compared with this reference example 1, less based on the resistance value climbing energetically containing the embodiment of Ti-of the present invention (Al+Si)-(N+O) based material of aerobic, thermal endurance is more excellent.
In addition, Ta-Al-N based material as compared to Ti with Al, Si very large due to the ionic radius of Ta, therefore cannot make wurtzite-type phase in high concentration Al region.Think because Ta-Al-N system is not wurtzite-type phase, therefore the thermal endurance that Ti-(Al+Si)-N is or Ti-(Al+Si)-(N+O) is of wurtzite-type phase is better.
[table 4]
In addition, technical scope of the present invention is not limited to above-mentioned execution mode and embodiment, without departing from the scope of spirit of the present invention, and can various change in addition.
Such as, in above-described embodiment, be set to M=Ti or Cr and made the thermistor metal nitride materials of M-(Al+Si)-(N+O), but for Ti or Cr at least partially, the at least one of V, Mn, Fe, Co can be replaced, same characteristic can be obtained.
Symbol description
1-film-type thermistor (temperature) sensor, 2-insulating properties film, 3-thin-film thermistor portion, 4,124-pattern electrode.

Claims (6)

1. a thermistor metal nitride materials, it is the metal nitride materials for thermistor, it is characterized in that,
By with general formula: M x(Al 1-vsi v) y(N 1-wo w) zthe metal nitride represented is formed, wherein, M represents at least one in Ti, V, Cr, Mn, Fe and Co, 0.0 < v < 0.3,0.70≤y/ (x+y)≤0.98,0.45≤z≤0.55,0 < w≤0.35, x+y+z=1
The crystalline texture of described thermistor metal nitride materials is the single-phase of the wurtzite-type of hexagonal crystal system.
2. thermistor metal nitride materials according to claim 1, is characterized in that,
Described thermistor metal nitride materials is formed as membranaceous,
And be the column crystallization extended along the direction perpendicular to the surface of described film.
3. thermistor metal nitride materials according to claim 1 and 2, is characterized in that,
Described thermistor metal nitride materials is formed as membranaceous,
On the direction on the surface perpendicular to described film, the orientation of c-axis is better than the orientation of a axle.
4. a film-type thermistor (temperature) sensor, is characterized in that, possesses:
Insulating properties film;
Thin-film thermistor portion, the thermistor metal nitride materials on this insulating properties film according to any one of claims 1 to 3 is formed; And
A pair pattern electrode, is at least formed in upside or the downside in described thin-film thermistor portion.
5. a manufacture method for thermistor metal nitride materials, is characterized in that, it is the method for the thermistor metal nitride materials according to any one of manufacturing claims 1 to 3,
Have the film formation process using M-Al-Si alloy sputtering targets to carry out reactive sputtering and film forming in the atmosphere of nitrogenous and oxygen, wherein, M represents at least one in Ti, V, Cr, Mn, Fe and Co.
6. the manufacture method of thermistor metal nitride materials according to claim 5, is characterized in that,
Sputtering pressure in described reactive sputtering is set smaller than 0.67Pa.
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